Functionalized initiators for anionic polymerization

ABSTRACT

A process for the preparation of hydrocarbon solutions of monofunctional ether initiators of the following general structure: 
     
         M--Z--O--C(R.sup.1 R.sup.2 R.sup.3) 
    
     wherein M is an alkali metal; Z is a branched or straight chain hydrocarbon group which contains 3-25 carbon atoms, optionally containing aryl or substituted aryl groups; and R 1 , R 2 , and R 3  are independently selected from hydrogen, alkyl, substituted alkyl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups, aryl or substituted aryl groups containing lower alkoxy, lower alkylthio, and lower dialkylamino groups, and their employment as initiators in the anionic polymerization of olefin containing monomers in an inert, hydrocarbon solvent comprising reacting an omega-protected-1-haloalkyl with lithium metal dispersion having a particle size between 10 and 300 millimicrons in size, at a temperature between 35° and 130° C. in an alkane solvent containing 5 to 10 carbon atoms.

This application is related to provisional application Ser. No.60/009,377, filed Dec. 29, 1995, now abandoned, and is acontinuation-in-part of U.S. Ser. No. 08/436,784, filed May 8, 1995, nowU.S. Pat. No. 5,621,149, which application is a continuation-in-part ofU.S. Ser. No. 08/332,217, filed Oct. 31, 1994, now abandoned.

This invention concerns novel anionic initiators for use in polymerizingolefinic-containing monomers, a process for making the anionicinitiators, a process for the polymerization of olefinic-containingmonomers using the anionic initiators of this invention and polymersproduced by this polymerization process.

Useful polymeric products are obtained by polymerizingolefinic-containing monomers in the presence of an organo-alkali metalinitiator and subsequently reacting the resulting polymer, containing anactive alkali metal end group or groups, with a reagent which willcouple the polymer molecules or replace the alkali metal with morestable reactive end groups.

Monofunctional silyl ether initiators, containing alkali metal endgroups useful in effecting such polymerization reactions are disclosedin Great Britain published patent application 2,241,239, published Aug.28, 1991. These monofunctional silyl ether initiators were demonstratedto be useful in producing polydienes having desirable characteristicssuch as a molecular weight of typically 1,000 to 10,000, 1, 4 content oftypically 90%, etc.

Although analogous lithiohydrocarbyl ether compounds have been preparedand utilized in organic syntheses by M. Gardette et al, Tetrahedron, 41,5887 1985!, these were prepared in ethereal solvents only, wherein theirstability was poor and their utility as polymer initiatorsdisadvantageous because of high solvent polarity.

The present invention provides a process for the preparation of novel,hydrocarbon solutions of monofunctional ether initiators of thefollowing general structure:

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)                         I!

wherein M is defined as an alkali metal, preferably lithium; Z is abranched or straight chain hydrocarbon tether group which contains 3-25carbon atoms, optionally containing aryl or substituted aryl groups; andR¹ R² and R³ are independently defined as H, alkyl, substituted alkylgroups containing lower alkoxy, lower alkylthio, and lower dialkylaminogroups, aryl or substituted aryl groups containing lower alkoxy, loweralkylthio, and lower dialkylamino groups, and their employment asinitiators in the anionic polymerization of olefin containing monomersin an inert, hydrocarbon solvent, optionally containing a Lewis Base.The process reacts selected protected omega-protected-1-haloalkyls whosealkyl groups contain 3 to 25 carbon atoms, which are reacted with analkali metal such as lithium, sodium or potassium in a liquid alkane,cycloalkane or aryl solvent, at a temperature between about 35° C. andabout 130° C.

The initiator precursor omega-protected 1-haloalkyls (halides) areprepared from the corresponding haloalcohol by the standard literaturemethods. For example, 3-(1,1-dimethylethoxy)-1-chloropropane issynthesized by the reaction of 3-chloro-1-propanol with 2-methylpropeneaccording to the method of A. Alexakis, M. Gardette, and S. Colin,Tetrahedron Letters, 29, 1988, 2951. The method of B. Figadere, X.Franck and A. Cave, Tetrahedron Letters, 34, 1993, 5893, which involvedthe reaction of the appropriate alcohol with 2-methyl-2-butene catalyzedby boron trifluoride etherate is employed for the preparation of thet-amyl ethers. The triphenylmethyl protected compounds, for example3-(triphenylmethoxy)-1-chloropropane, are prepared by the reaction ofthe haloalcohol with triphenylmethylchloride, according to the method ofS. K. Chaudhary and O. Hernandez, Tetrahedron Letters, 1979, 95. Thecompound 4-(methoxy)-1-chlorobutane, and the higher analogues, aresynthesized by the ring opening reaction of tetrahydrofuran with thionylchloride and methanol, according to the procedure of T. Ferrari and P.Vogel, SYNLETT, 1991, 233.

Monofunctional ether initiators (I) are prepared in accord with theprocess of this invention and such compounds can include, but are notlimited to, 3-(1,1-dimethylethoxy)-1-propyllithium,5-(1,1-dimethylethoxy)-1-pentyllithium,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propyllithium, 4-(1,1-dimethylethoxy)-1-butyllithium,6-(1,1-dimethylethoxy)-1-hexyllithium,8-(1,1-dimethylethoxy)-1-octyllithium, 4-(ethoxy)-1-butyllithium,4-(1-propyloxy)-1-butyllithium, 4-(1-methylethoxy)-1-butyllithium,3-(triphenylmethoxy)-2,2-dimethyl-1-propyllithium,4-(triphenylmethoxy)-1-butyllithium,5-(triphenylmethoxy)-1-pentyllithium,6-(triphenylmethoxy)-1-hexyllithium,8-(triphenylmethoxy)-1-octyllithium,3-(1,1-dimethylpropyloxy)-1-propyllithium,3-(1,1-dimethylpropyloxy)-2,2-dimethyl-1-propyllithium,4-(1,1-dimethylpropyloxy)-1-butyllithium, 3-3-(dimethylamino)-1-propyloxy!-1-propyllithium, 3-2-(dimethylamino)-1-ethoxy!-1-propyllithium, 3-2-(diethylamino)-1-ethoxy!-1-propyllithium, 3-2-(diisopropyl)amino)-1-ethoxy!-1-propyllithium, 3-2-(1-piperidino)-1-ethoxy!-1-propyllithium, 3-2-(1-pyrrolidino)-1-ethoxy!-1-propyllithium, 4-3-(dimethylamino)-1-propyloxy!-1-butyllithium, 6-2-(1-piperidino)-1-ethoxy!-1-hexyllithium, 3-2-(methoxy)-1-ethoxy!-1-propyllithium, 3-2-(ethoxy)-1-ethoxy!-1-propyllithium, 4-2-(methoxy)-1-ethoxy!-1-butyllithium, 5-2-(ethoxy)-1-ethoxy!-1-pentyllithium, 3-3-(methylthio)-1-propyloxy!-1-propyllithium, 3-4-(methylthio)-1-butyloxy!-1-propyllithium,3-(methylthiomethoxy)-1-propyllithium, 6-3-(methylthio)-1-propyloxy!-1-hexyllithium, 3-4-(methoxy)-benzyloxy!-1-propyllithium, 3-4-(1,1-dimethylethoxy)-benzyloxy!-1-propyllithium, 3-2,4-(dimethoxy)-benzyloxy!-1-propyllithium, 8-4-(methoxy)-benzyloxy!-1-octyllithium, 4-4-(methylthio)-benzyloxy!-1-butyllithium, 3-4-(dimethylamino)-benzyloxy!-1-propyllithium, 6-4-(dimethylamino)-benzyloxy!-1-hexyllithium,6-(1,1-dimethylpropyloxy)-1-hexyllithium, 4-methoxy-1-butyllithium,3-methoxy-1-butyllithium, 3-(triphenylmethoxy)-1-propyllithium,3-(1,1-dimethylethoxy)-2-methyl-1-propyllithium, and3-(1,1-dimethylpropyloxy)-2-methyl-1-propyllithium.

Alkali metal used in preparing the monofunctional ether initiators (I)is used as a dispersion whose particle size usually does not exceedabout 300 microns. Preferably the particle size is between 10 and 300microns although coarser particle size alkali metal can be used. Whenthe alkali metal is lithium, the lithium metal can contain 0.2 to 0.8and preferably 0.3 to 0.5 weight percent sodium. The lithium metal isused in amounts of 90% of theoretical to a 40% excess above thetheoretical amount necessary to produce the monofunctional etherinitiators (I).

The preferred reaction temperatures vary from compound to compound, witheach compound tending to have its own preferred reaction conditions.Suprisingly, for some compounds the preferred reactontemperature/condition is the reflux temperature of the solvent. Whenthis is the case the preferred reaction temperature is in the range of35° to 80° C.

Solvents useful in practicing this invention include but are not limitedto inert liquid alkanes, cycloalkanes and aryl solvents such as alkanesand cycloalkanes containing five to 10 carbon atoms such as pentane,hexane cyclohexane methylcyclohexane, heptane, methylcycloheptane,octane, decane and so forth and aryl solvents containing six to tencarbon atoms such as toluene, ethylbenzene, p-xylene, m-xylene,o-xylene, n-propylbenzene, isopropylbenzene, n-butylbenzene,and thelike.

Advantages of using the compounds containing the protecting groups ofthis invention comprising the process of producing a lithium initiatorand subsequently in using the said initiator to produce polymerscontaining the said protecting groups as compared to using substitutedsilyl protecting groups are as follows: 1) cheaper and more readilyavailable raw materials are used in the preparation of initiators, e.g.inexpensive olefins such as isobutylene or isoamylene are reacted withomega halo-alcohol as compared to the use of the more expensive alkylchlorosilanes, such as tert-butyldimethylchlorosilane ordiphenylmethylchlorosilane. 2) The excellent stability of the protectivegroup to most reagents except strong acids comparable totert-butyldimethylsilyl group! 3) The protecting groups of thisinvention can be removed in as many ways and as simply as any of thesubstituted silyl protecting groups. Thus, for example, a tert-butylprotecting group on a hydroxy terminated polymer can be removed with a)anhydrous triflic acid b) HBr in acetic acid c) HCl in dioxane d) aceticanhydride in ethyl ether (FeCl3 catalyst) e) TiCl4 in CH2Cl2 ( T. W.Greene, Protective Groups in Organic Chemistry, Wiley, N.Y., 1981, pp41-42) f) catalytic amounts of tert-butyldimethylsilyl triflate inmethylene chloride (X. Frank et al, Tetrahedron Letters, 36, (5), 711(1995). g) Amberlyst acidic ion exchange resin may also be employed atelevated temperatures. 4) The by-products of the deprotection step areeasy to remove from the polymer. For example, the by-product of thedeprotection reaction of the tert-butyl protected hydroxypolymer isisobutylene, which is innocuous and does not require removal from thepolymer, although it can be removed easily at temperatures above 100degrees C during deprotection (see U.S. Pat. No. 4,886,446). Theby-product of the deprotection of an alkylsilyl protected hydroxypolymer is an alkylsiloxane which is a contaminant that may requireremoval from the polymer.

Anionic polymerizations employing the herein described monofunctionalether initiators of this invention are conducted in an inert solvent,preferably a non-polar solvent, optionally containing an etherealmodifier, using an olefinic monomer which is an alkene or a 1,3-diene ata temperature of about -30° C. to about +100° C. The polymerizationreaction proceeds from initiation to propagation and finally terminationso that the polymer is mono-functional or difunctionally terminated. Thepolymers have molecular weight ranges of about 1000 to 10,000. Typically5 to 50 millimoles of initiator is used per mole of monomer.

The present invention also provides a process for the anionicpolymerization of anionically pollymerizable monomers comprising thesteps of:

a) initiating polymerization of a conjugated diene hydrocarbon monomeror an alkenylsubstituted aromatic hydrocarbon monomer in a hydrocarbonor mixed hydrocarbon-polar solvent medium at a temperature of 10° C. to70° C. with an initiator having the formula:

    M--Z--OC(R.sup.1 R.sup.2 R.sup.3)                          (II)

wherein M is an alkali metal, preferably lithium, Z is a branched orstraight chain hydrocarbon tether or connecting group which contains3-25 carbon atoms, optionally containing aryl or substituted arylgroups; and R¹, R², and R³ are independently selected from hydrogen,alkyl, substituted alkyl groups containing lower alkoxy, loweralkylthio, and lower dialkylamino groups, aryl or substituted arylgroups containing lower alkoxy, lower alkylthio, and lower dialkylaminogroups to produce an intermediate polymer of formula Li--(Q)m--Z--OC(R¹R² R³) wherein Q is a unit of polymerized conjugated diene oralkenylsubstituted aromatic hydrocarbon and Z, R¹ R² and R³ have themeanings ascribed above, m is the number of units ot the polymerizedconjugated diene or alkenylsubstitiuted aromatic hydrocarbon and mayvary from 10 to 200 units: reacting the intermediate polymer with acompound selected from ethyene oxide, oxygen, carbon dioxide, sulfur,omega-alkenylarylhalosilanes (as exemplified bystyrenyidimethylchlorosilane), isomeric divinylbenzenes, chiorosilanes(as exemplified by silicon tetrachloride and dimethyldichlorosilane, andchlorostannanes (as exemplified by tin tetrachloride and dibutyltindichloride) and other materials known in the art to be useful forterminating, end capping or coupling of polymers; optionallyhydrogenating the polymer; and

b) recovering a linear or branched polymer having one or more terminalfunctional groups, having the formula FG--(Q)m--Z--OC(R1R2R3) wherein FGis a functional group derived by reaction of the intermediate polymerwith one of the selected functionalizing compounds described above and mis the number of units of the polymerized conjugated diene oralkenylsubstituted aromatic hydrocarbon and may vary from 10 to 200

c) further reacting the functional polymer with other comonomers such asdiesters, diisocyanates, di- or cyclic amides, and diols in the presenceof a strong acid catalyst to simultaneously deprotect the fuctionalpolymer and polymerize both functional ends thereof to produce novelsegmented block polymers, or

d) further reacting the functional polymer with other comonomers in theabsence of a strong acid catalyst to yield novel block polymers, whilemaintaining the integrity of the protective group, or

e) further removing the protective group from the resultant polymer fromd) above followed by reaction with the same or other comonomers toproduce novel segmented block polymers.

The olefinic monomer to be anionically polymerized by the monofunctionalether initiator is preferably a conjugated diene or an alkenylaromatichydrocarbon The conjugated diene or alkenylaromatic compound will bechosen from the group of unsaturated organic compounds that can bepolymerized anionically (i.e., in a reaction initiated by anorgano-alkali metal). Suitable alkenylaromatics include theoptionally-substituted styrenes and vinyinaphthalenes.Alkenylsubstituted aromatic hydrocarbons useful in practicing thisinvention include but are not limited to styrene, alpha-methylstyrene,vinyltoluene, 1-vinylnapthalene, 3-methylstyrene, 4-methylstyrene,1,1-diphenylethylene and the like. Suitable 1,3-dienes will preferablycontain from 4 to 12, especially from 4 to 8, carbon atoms per molecule.Examples of these compounds include, but are not limited to, thefollowing: 1,3-butadiene, isoprene; 2,3-dimethyl-1,3-butadiene,1,3-pentadiene, 2-methyl-3-ethyl-1,3-butadiene,2-methyl-3-ethyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-hexadiene,1,3-heptadiene, 3-methyl-1,3-heptadiene, 1,3-octadiene,3-butyl-1,3-octadiene, 3,4-dimethyl-1,3-hexadiene;3-n-propyl-1,3-pentadiene, 4,5-diethyl-1,3-octadiene,2,4-diethyl-1,3-butadiene, 2,3-di-n-propyl-1,3-butadiene,2,5-dimethyl-2,4-hexadiene and 2-methyl-3-isopropyl-1,3-butadiene.

Among the dialkylbutadienes, it is preferred that the alkyl groupscontain from 1 to 3 carbon atoms. Of the above monomers 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene are preferredwith 1,3-butadiene being particularly preferred. The dienes may bepolymerised alone, or in admixture with each other or withalkenylaromatic compounds to form random copolymers, or by charging thedienes to the reaction mixture sequentially, either with each other orwith alkenylaromatic compounds, to form block copolymers

For example, a protected functional living polymer of this invention canbe generated by polymerizing 1,3-butadiene with an initiator of formulaI above, wherein M is lithium, Z is a trimethylene tether or connectinggroup, and R¹, R², and R³ are methyl groups. A living polymer isproduced having the formula

    Li--(B)m--(CH.sub.2).sub.3 --O--C(CH.sub.3).sub.3          (III)

where B is a unit derived by polymerizing butadiene, and m is an integerfrom about 10 to 200. The living polymer III, may be reacted, forexample, with ethylene oxide to yield, after hydrolysis, the compound offormula

    HOCH2CH2--(B)m--(CH.sub.2).sub.3 --O--C(CH.sub.3).sub.3    (IV)

which may optionally be hydrogenated to the corresponding asymmetricpolymer.

Additionally, other asymmetrically difunctional polymers may be producedby reacting the living polymer (III) above with, for example, carbondioxide to produce, a polymer with one protected hydroxyl and onecarboxyl group, or the living polymer III may be reacted with 1,5diazabicyclo-(3.1.0) hexane as described in U.S. Pat. No. 4,753,991 toproduce a polymer with one protected hydroxyl and one amino group.

Other asymmetrically substituted monofunctional polymers may be producedhaving epoxy or isocyanate groups at one end for example by reacting thelithium salt of IV above (before hydrolysis), with epichlorohydrin or,by reacting IV itself with an equivalent of a diisocyanate, such asmethylene 4,4-diphenyl diisocyante (2/1 NCO/OH). These unsymmetricallysubstituted difunctional polymers could then be further reacted withother comonomers either with or without simultaneous deprotection asdescribed above.

The protected monohydroxy polymers (IV) alone and in their hydrogenatedforms, could be used as base materials to lend flexibility and higherimpact strength in a number of formulas to produce coatings, sealants,binders and block copolymers with polyesters, polyamides andpolycarbonates as described in UK Patent Application GB2270317A and in"Polytail" data sheets and brochures (Mitsubishi Kasei America).

Thus, in the presence of acidic catalysts used to promote the formationof many of these block copolymer resins, the protective group of thehydrogenated polymer is removed as well, allowing the exposed hydroxylgrouping in the base polymer molecule to simultaneously participate inthe block copolymer reaction.

Thus, for example, hydrogenated IV polymers may be reacted withbisphenol A and phosgene in the presence of appropriate catalysts withsimultaneous deprotection to yield a polycarbonate alternating blockcopolymer. The resulting products are useful as molding resins, forexample, to prepare interior components for automobiles.

A segmented polyamide-hydrogenated IV block copolymer also useful as amolding composition to prepare exterior automotive components can beprepared by reacting hydrogenated IV polymer with caprolactam and adipicacid in the presence of a suitable catalyst.

A segmented polyester-hydrogenated IV block copolymer can be produced byreaction of hydrogenated IV polymer with dimethyl terephthalate and asuitable acidic catalyst. Again, the products are useful as moldingcompounds for exterior automotive components.

Isocyanate-terminated prepolymers can be produced from hydrogenated IVpolymers by reaction with suitable diisocyanates (2/1 NCO/OH) as abovewhich can be further reacted with diols and additional diisocyanates toform segmented polyurethanes useful for water based, low VOC coatings.Or segmented polyurethane prepolymers may be mixed with tackifyingresins and used as a moisture-curable sealant, caulk or coating.

An acrylate-terminated prepolymer curable by free-radical processes canbe prepared from the hydrogenated IV polymer by reaction with adiisocyanate (2NCO/OH) followed by further reaction with hydroxyethylacrylate in the presence of a basic reagent.

Alternatively, the protected monohydroxy terminated polymer (IV) may bereacted with functional comonomers, wihout simultaneously removing theprotective group, to produce novel copolymers. These copolymers may bedeprotected and then further reacted with the same or differentcomonomers to form yet other novel copolymers. Thus, for example, thehydroxyterminated polymer of formula (IV) may be hydrogenated, and thenreacted with ethylene oxide in the presence of potassium tert-butoxideto produce a poly(ethleneoxide)-hydrogenated polybutadiene copolymerwith one protected hydroxyl group on the polybutadiene segment. Thishydroxyl can then be deprotected and a poly(ethyleneoxide) polymerhaving different chain lengths grown onto both ends of the polybutadienesegment.

These processes can be applied to the deprotected and optionallyhydrogenated polymers of formula IV, as well.Thus,alternatively, theprotective group could be removed first from the hydrogenated polymer,and then the block copolymers formed by addition of the appropriatecomonomers.

In another possible application, the living polymer III may be reactedwith an alkenylarylhalosilane such as styrenyldimethylchlorosilane toyield the correspcnding omega-styrenylterminated macromonomer accordingto directions in U.S. Pat. No. 5,278,244 which may be furtherpolymerized by a variety of techniques to yield "comb" polymers which,on deprotection and hydrogenation yield branched polymers withhydroxyfunctionality on the branch-ends. Such multi-functionality can beutilized to graft a watersoluble polymer such as polyethylene oxide ontoa hydrophobic polyolefinic core to produce hydrogels.

In still another example, a living polymer analogous to III having theformula

    Li(B)x(S)y(CH2)3--OC(CH3)3

where B is polymerized butadiene, S is polymerized styrene and x and ycan vary from 10 to 1000 or more is reacted with divinylbenzene (DVB) toproduce a multi-armed star polymer, according to U.S. Pat. No. 4,409,357which on hydrogenation and deprotection would yield a star withhydroxy-functional branches which may be further reacted with ethyleneoxide and potassium alkoxide as described above to produce hydrogels.

In still another possible application, the hydrogenatedhydroxyterminated branches of the star polymer may be further reactedwith acryloyl chloride or methacryloyl chloride, and the resultantacrylate or methacrylate-terminated polymer further polymerized withmonomers selected from the group of alkyl acrylates, alkylmethacrylates, and dialkylacrylamides to produce hydrogels. Starpolymers are useful as viscosity index improver for motor oils.

Other monomers may be reacted directly with formula III type compoundsto yield block or star copolymers.

The following examples further illustrate the invention.

EXAMPLE 1 PREPARATION OF 3-(1,1-DIMETHYLETHOXY)-1-PROPYLLITHIUM INCYCLOHEXANE, LOT 8888

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8200, 0.61% sodium, was washed freeof mineral oil with hexane (2×70 ml), and pentane (1×70 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(4.07 grams, 0.586 mole, 2.80 equivalents), and transferred to thereaction flask with 150 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 70° C. with a heating mantle. Theheat source was removed. 1-Chloro-3-(1,1-dimethylethoxy)-propane, 31.52grams, (0.209 mole, 1.00 equivalent, lot 8864) was added dropwise viathe addition funnel. An exotherm was detected after 5.5% of the halidefeed had been added. A dry ice/hexane cooling bath was applied as neededto maintain the reaction temperature between 60°-65° C. The total halidefeed time was fifty-two minutes. The cooling bath was removed at the endof the halide feed. The reaction temperature fell off rapidly to roomtemperature. The reaction mixture was stirred for one hour at 450 RPMs,and two and one half hours at 300 RPMs. The reaction mixture wastransferred with argon pressure to a dry sintered glass pressure filter.The product solution was pressure filtered with 3 psi (20.68×10³ Pa)argon. The lithium chloride muds were reslurried with fresh cyclohexane(2×50 ml.). The filtrate was a clear, yellow solution, yield=230 ml.,185.03 grams.

Total Base=3.85 wt. %. Active C--Li=3.78 wt. %. Yield=27.4% (based onactive analysis).

A one ml. aliquot of this solution was carefully quenched with water.The organic phase was analyzed by Gas Chromatography (30 m.×0.54 mm AT-1column). 1-Chloro-3-(1,1-dimethylethoxy)-propane (retention time=13.58minutes) was not detected. The corresponding des-chloro material(retention time=8.36 minutes) was identified by GC/MS.

The very thick lithium chloride mud cake was washed with drydibutylether (3×50 ml.). This afforded a clear, colorless solution,yield=200 ml., 154.76 grams.

Total Base=5.69 wt %. Active C--Li=3.32 wt. %. Yield=20.1% (based onactive analysis).

The total yield was 47.6%.

EXAMPLE 2 PREPARATION OF3-(1,1-DIMETHYLETHOXY)-2,2-DIMETHYL-1-PROPYLLITHIUM IN CYCLOHEXANE, LOT8923

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8200, 0.61% sodium, was washed freeof mineral oil with hexane (2×70 ml), and pentane (1×70 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(4.40 grams, 0.634 mole, 2.80 equivalents), and transferred to thereaction flask with 200 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 65° C. with a heating mantle. Theheat source was removed.1-Chloro-3-(1,1-dimethylethoxy)-2,2-dimethyl-propane, 40.42 grams,(0.226 mole, 1.00 equivalent, lot 8913) was added dropwise via theaddition funnel. An exotherm was detected after 12.8% of the halide feedhad been added. A dry ice/hexane cooling bath was applied as needed tomaintain the reaction temperature between 60°-65° C. The total halidefeed time was one hour. The cooling bath was removed at the end of thehalide feed. The reaction temperature fell off rapidly to roomtemperature. The reaction mixture was stirred for eighty minutes at 450RPMs. The reaction mixture was then transferred with argon pressure to adry sintered glass pressure filter. The product solution was pressurefiltered with 3 psi (20.68×10³ Pa) argon. The lithium chloride muds werereslurried with fresh cyclohexane (2×40 ml.). The filtrate was a clear,pale yellow solution, yield=320 ml., 251.91 grams. A white solidprecipitated from solution immediately after the filtration.

Analysis of the supernatant solution: Total Base=7.4 wt. %. ActiveC--Li=7.0 wt. %. Yield=52.0% (based on active analysis). Analysis of theslurry:

Total Base=12.4 wt. %. Active C--Li=11.9 wt. %. Yield=88.4% (based onactive analysis).

EXAMPLE 3 PREPARATION OF 3-(1,1-DIMETHYLPROPYLOXY)-1-PROPYLLITHIUM INCYCLOHEXANE, LOT 9135

A one liter, three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8899, 0.43% sodium, was washed freeof mineral oil with hexane (2×100 ml), and pentane (1×100 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(6.35 grams, 0.915 mole, 3.67 equivalents), and transferred to thereaction flask with 180 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 65° C. with a heating mantle. Theheat source was removed. 1-Chloro-3-(1,1-dimethylpropyloxy)-propane,41.00 grams, (0.249 mole, 1.00 equivalent, lot 9118, 9134) was addeddropwise via the addition funnel. An exotherm was detected after 13% ofthe feed had been added. A dry ice/hexane cooling bath was applied asneeded to maintain the reaction temperature between 60°-65° C. The totalhalide feed time was sixty-five minutes. The cooling bath was removed atthe end of the halide feed. The reaction temperature fell off graduallyto room temperature. The reaction mixture was stirred for one hour at450 RPMs, and one hour at 300 RPMs. The reaction mixture was transferredwith argon pressure to a dry sintered glass pressure filter. The productsolution was pressure filtered with 3 psi (20.68×10³ Pa) argon. Thelithium chloride muds were reslurried with fresh cyclohexane (2×50 ml.).The filtrate was a clear, pale yellow solution, yield=250 ml., 190.86grams.

Total Base=6.32 wt. %. Active C--Li=5.01 wt. %. Yield=28.2% (based onactive analysis).

EXAMPLE 4 PREPARATION OF3-(1,1-DIMETHYLPROPYLOXY)-2,2-DIMETHYL-1-PROPYLLITHIUM IN CYCLOHEXANE,LOT 9167

A one liter, three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8899, 0.43% sodium, was washed freeof mineral oil with hexane (2×100 ml), and pentane (1×100 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(3.33 grams, 0.480 mole, 2.86 equivalents), and transferred to thereaction flask with 150 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 65° C. with a heating mantle. Theheat source was removed1-Chloro-3-(1,1-dimethylpropyloxy)-2,2-dimethyl-propane, 33.00 grams,(0.168 mole, 1.00 equivalent, lot 9152) was added dropwise via theaddition funnel. An exotherm was detected after 22% of the halide feedhad been added. A dry ice/hexane cooling bath was applied as needed tomaintain the reaction temperature between 60°-65° C. The total halidefeed time was fifty-three minutes. The cooling bath was removed at theend of the halide feed. The reaction temperature fell off gradually toroom temperature. The reaction mixture was stirred for forty-fiveminutes at 450 RPMs, and seventy-five minutes at 300 RPMs. The reactionmixture was transferred with argon pressure to a dry sintered glasspressure filter. The product solution was pressure filtered with 3 psi(20.68×10³ Pa) argon. The lithium chloride muds were reslurried withfresh cyclohexane (2×50 ml.). The filtrate was a clear, pale yellowsolution, yield=250 ml., 194.93 grams.

Total Base=12.4 wt. %. Active C--Li=11.3 wt. %. Yield=78.3% (based onactive analysis).

EXAMPLE 5 PREPARATION OF 4-METHOXY-1-BUTYLLITHIUM IN CYCLOHEXANE LOT8916

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8200, 0.61% sodium, was washed freeof mineral oil with hexane (2×70 ml), and pentane (1×70 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(7.25 grams, 1.045 mole, 2.80 equivalents), and transferred to thereaction flask with 200 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 72.6° C. with a heating mantle. Theheat source was removed. 1-Chloro-4-methoxy-butane, 45.70 grams, (0.373mole, 1.00 equivalent, lot 8663) was added dropwise via the additionfunnel. An exotherm was detected after 7.8% of the feed had been added.Hexane/dry ice cooling was applied to maintain the reaction temperatureat 60°-65° C. The total halide feed time was sixty-five minutes. Thecooling bath was removed at the end of the halide feed. The reactiontemperature fell off rapidly to room temperature. The reaction mixturewas stirred for one hour at 450 RPMs. The reaction mixture was thentransferred with argon pressure to a dry sintered glass pressure filter.The product solution was pressure filtered with 3 psi (20.68×10³ Pa)argon. The lithium chloride muds were reslurried with fresh cyclohexane(2×40 ml.). The filtrate was a clear, very pale yellow solution,yield=300 ml., 242.28 grams.

Total Base=12.4 wt. %. Active C--Li=12.1 wt. %. Yield=83.6% (based onactive analysis).

EXAMPLE 6 PREPARATION OF 3-METHOXY-1-BUTYLLITHIUM IN CYCLOHEXANE, LOT8939

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8899, 0.43% sodium, was washed freeof mineral oil with hexane (2×70 ml), and pentane (1×70 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(6.35 grams, 0.915 mole, 2.80 equivalents), and transferred to thereaction flask with 200 ml of cyclohexane. The reaction mixture wasstirred at 450 PPMs, and heated to 68° C. with a heating mantle. Theheat source was removed. 1-Chloro-3-methoxy-butane, 40.03 grams, (0.327mole, 1.00 equivalent, lot 8914) was added dropwise via the additionfunnel. An exotherm was detected after 7.5% of the feed had been added.A dry ice/hexane cooling bath was applied as needed to maintain thereaction temperature between 60°-65° C. The total halide feed time waseighty-three minutes. The cooling bath was removed at the end of thehalide feed. The reaction temperature fell off rapidly to roomtemperature. The reaction mixture was stirred for one hour at 450 RPMs.The reaction mixture was then transferred with argon pressure to a drysintered glass pressure filter. The product solution was pressurefiltered with 3 psi (20.68×10³ Pa) argon. The lithium chloride muds werereslurried with fresh cyclohexane (2×75 ml.). The filtrate was a clear,pale yellow solution, yield=280 ml., 215.70 grams.

Total Base=13.58 wt. %. Active C--Li=13.12 wt. %. Yield=92.1% (based onactive analysis). Soluble chloride=62 ppm.

EXAMPLE 7 PREPARATION OF 4-(2-BUTOXY)-1-BUTYLLITHIUM IN CYCLOHEXANE, LOT8956

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8899, 0.43% sodium, was washed freeof mineral oil with hexane (2×100 ml), and pentane (1×100 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(6.70 grams, 0.965 mole, 2.80 equivalents), and transferred to thereaction flask with 250 ml of cyclohexane The reaction mixture wasstirred at 450 RPMs, and heated to 65° C. with a heating mantle. Theheat source was removed. 4-(2-Butoxy)-1-chloro-butane, 56.72 grams,(0.345 mole, 1.00 equivalent, lot 8921) was added dropwise via theaddition funnel. An exotherm was detected after 15.6% of the halide feedhad been added. A dry ice/hexane cooling bath was applied as needed tomaintain the reaction temperature between 60°-65° C. The total halidefeed time was seventy-two minutes. The cooling bath was removed at theend of the halide feed. The reaction temperature fell off rapidly toroom temperature. The reaction mixture was stirred for one hour at 450RPMs. The reaction mixture was then transferred with argon pressure to adry sintered glass pressure filter. The product solution was pressurefiltered with 3 psi (20.68×10³ Pa) argon. The lithium chloride muds werereslurried with fresh cyclohexane (1×75 ml., 1×50 ml.). The filtrate wasclear, yellow solution, yield=440 ml., 348.84 grams.

Total Base=12.1 wt. %. Active C--Li=11.2 wt. %. Yield=83.3% (based onactive analysis).

EXAMPLE 8 PREPARATION OF 4-(1-METHYLETHOXY)-1-BUTYLLITHIUM INCYCLOHEXANE, LOT 9042

A 500 ml., three-necked, Morton flask was fitted with a mechanicalstirrer, a 125 ml pressure-equalizing addition funnel, and a Claisenadapter equipped with a thermocouple, a dry ice condenser, and an argoninlet. This apparatus was dried in an oven overnight at 125° C.,assembled hot, and allowed to cool to room temperature in a stream ofargon. Lithium metal dispersion, lot 8899, 0.43% sodium, was washed freeof mineral oil with hexane (2×70 ml), and pentane (1×70 ml). Theresultant lithium dispersion was dried in a stream of argon, weighed(6.00 grams, 0.864 mole, 2.80 equivalents), and transferred to thereaction flask with 250 ml of cyclohexane. The reaction mixture wasstirred at 450 RPMs, and heated to 80° C. with a heating mantle. Theheat source was removed. 1-Chloro-4-(1-methylethoxy)-butane, 46.47grams, (0.309 mole, 1.00 equivalent, lot 8960) was added dropwise viathe addition funnel. An exotherm was detected after 22.9% of the halidefeed had been added. A dry ice/hexane cooling bath was applied as neededto maintain the reaction temperature between 60°-65° C. The total halidefeed time was forty-five minutes. The cooling bath was removed at theend of the halide feed. The reaction temperature fell off rapidly toroom temperature. The reaction mixture was stirred for ninety minutes at450 RPMs, then for two hours at 300 RPMs. The reaction mixture was thentransferred with argon pressure to a dry sintered glass pressure filter.The product solution was pressure filtered with 3 psi (20.68×10³ Pa)argon. The lithium chloride muds were reslurried with fresh cyclohexane(2×25 ml.). The filtrate was a clear, yellow solution, yield=350 ml.,264.91 grams.

Total Base=12.3 wt. %. Active C--Li=11.0 wt. %. Yield=77.3% (based onactive analysis).

POLYMERIZATION EXAMPLE POLYMERIZATION OF ISOPRENE WITH4-METHOXY-1-BUTYLLITHIUM, LOT 8970

A one liter, three-necked, round-bottom flask was fitted with amechanical stirrer, a septum and a Claisen adapter equipped with athermocouple, dry ice condenser, and an argon inlet. This apparatus wasdried in an oven overnight at 125° C., assembled hot, and allowed tocool to room temperature in a stream of argon. The flask was chargedwith cyclohexane, 310.70 grams, and isoprene, 40.00 grams (0.587 mole).The reaction mixture was at 20.0° C. 4-Methoxy-1-butyllithium, 16.74grams of 11.4 wt. % solution (0.020 mole, Lot 8915) was then added witha syringe. An exotherm of 1° C. was detected. The clear solution washeated to 48.4° C. with a heating mantle. The heat source was removed.The reaction temperature proceeded to climb steadily to 53.4° C., atwhich time a dry ice/hexane cooling bath was employed for a few minutesto moderate the temperature. The cooling bath was then removed. Thereaction temperature gradually declined to 24.2° C. in one hour. Thereaction mixture was stirred at room temperature for sixteen hours, thenquenched with methanol (40 ml.) and hexane (100 ml.). The reactionmixture was transferred to a one liter separatory funnel, and themethanol layer was discarded. The hydrocarbon layer was washed with anadditional 40 ml. of methanol, and concentrated to constant weight onthe rotary evaporator, at a bath temperature of 35° C. This afforded aclear, somewhat viscous oil, yield=39.00 grams (97.3%).

VPO analysis, Mn=1996. GPC analysis, MWD=1.48.

The remaining polymerization data is collected in the Table.

PREPARATION OF STARTING MATERIALS

1. 1-CHLORO-3-(1,1-DIMETHYLETHOXY)-PROPANE, LOT 8864

A two liter, three-necked round bottom flask was fitted with amechanical stirrer, a gas inlet tube, and a Claisen adapter equippedwith a dry ice condenser, and a thermocouple This apparatus was dried inan oven overnight at 125° C., assembled hot, and allowed to cool to roomtemperature in a stream of argon. The flask was charged with 141.81grams (1.50 moles, 1.00 equivalent) of 3-chloro-1-propanol and 500 ml.of cyclohexane. The resultant two-phase solution was stirred at 400RPMs. Amberlyst 15 resin catalyst, 35 grams, was added, followed by anadditional 250 ml. of cyclohexane. A total of 93 grams (1.657 moles,1.105 equivalents) of 2-methylpropene was discharged from the cylinderin two and a third hours. A modest exotherm was noted during theaddition. The reaction mixture was stirred at 20°-25° C., andperiodically monitored by gas chromatography (GC) for the disappearanceof 3-chloro-1-propanol. After stirring at room temperature fortwenty-eight hours, the conversion to the desired product was 94.7%. Thecatalyst was removed by filtration through a piece of fluted filterpaper. The reaction flask was rinsed with fresh cyclohexane (2×100 ml.).The product was purified by distillation from 10.72 grams of potassiumcarbonate through a twelve inch Vigreux column, at atmospheric pressure.This afforded a clear, colorless oil, yield=158.42 grams (70.2%).

B.P.=151.0°-154.8° C. GC assay=0.59% 2-methylpropene, 2.54% cyclohexane,87.15% desired product, and 9.72% unknowns. NMR (CDCl₃): 3.63 (t, J=6Hz, 2H), 3.46 (t, J=6 Hz, 2H), 2.28-1.62 (m, 2H), 1.21 (s, 9H) ppm.

2. 1-CHLORO-3-(1,1-DIMETHYLETHOXY)-2,2-DIMETHYL-PROPANE, LOT 8913

A one liter, three-necked round bottom flask was fitted with amechanical stirrer, a gas inlet tube, and a Claisen adapter equippedwith a dry ice condenser, and a thermocouple. This apparatus was driedin an oven overnight at 125° C., assembled hot, and allowed to cool toroom temperature in a stream of argon. The flask was charged with 91.95grams (0.75 moles, 1.00 equivalent) of 3-chloro-2,2-dimethyl-1-propanoland 200 ml. of cyclohexane. The resultant one-phase solution was stirredat 400 RPMs. Amberlyst 15 resin catalyst, 15 grams, was added, followedby an additional 50 ml. of cyclohexane. A total of 48.4 grams (0.86moles, 1.15 equivalents) of 2-methylpropene was discharged from thecylinder in three and a half hours. A modest exotherm was noted duringthe addition. The reaction mixture was stirred at 20°-25° C., andperiodically monitored by gas chromatography (GC) for the disappearanceof 3-chloro-2,2-dimethyl-1-propanol. After stirring at room temperaturefor twenty hours, all the starting material had been consumed, with theformation of a single, higher-boiling compound. The catalyst was removedby filtration through a piece of fluted filter paper. The reaction flaskwas rinsed with fresh cyclohexane (2×50 ml.). The product was purifiedby distillation from 5.07 grams of potassium carbonate through a twelveinch Vigreux column, at atmospheric pressure. This afforded a clear,colorless oil, yield=111.21 grams (83.0%).

B.P.=169.0°-174.0° C. GC assay=2.98% cyclohexane, 16.79%3-chloro-2,2-dimethyl-1-propanol, 78.06% desired product, and 1.17%unknowns.

3. 1-CHLORO-3-(1,1-DIMETHYLPROPYLOXY)-PROPANE, LOT 9245

A 500 ml., three-necked round bottom flask was fitted with a refluxcondenser, a thermocouple, a septum inlet, a magnetic stir bar, and anargon inlet. The flask was charged with 3-chloro-1-propanol, 94.54 grams(1.00 mole, 1.00 equivalents), pentane (50 ml.), and 2-methyl-2-butene,70.44 grams (1.00 mole, 1.00 equivalents). This afforded a two phasesolution. The reaction mixture was maintained at 20°-25° C. with a watercooling bath. Boron trifluoride etherate, 13.85 grams (0.098 mole, 0.098equivalents) was added rapidly via syringe. A mild exotherm, 4°-5° C.,ensued, which subsided in fifteen minutes. The reaction mixture wasstirred at 20°-25° C., and periodically monitored by gas chromatography(GC) for the disappearance of 3-chloro-1-propanol. After forty-eighthours stirring, all the starting material had been consumed, and thereaction mixture was a single phase. The reaction mixture was dilutedwith pentane (100 ml.) and water (100 ml.) and transferred to aseparatory funnel. The aqueous layer was discarded. The organic layerwas washed with saturated sodium bicarbonate solution (2×50 ml.), water(1×50 ml.), and filter-dried over magnesium sulfate. The filtrate wasconcentrated on the rotary evaporator at room temperature to afford apale yellow liquid, yield=113.47 grams (69.0%).

GC assay=96.7% desired product, 3.3% unknowns. NMR (CDCl₃): 3.65 (t, J=6Hz, 2H), 3.45 (t, J=6 Hz, 2H), 2.00 (q, J=6 Hz, 2H), 1.80-1.25 (m, 2H),1.13 (s, 6H), and 0.84 (t, J=6 Hz, 3H) ppm.

4. 1-CHLORO-3-(1,1-DIMETHYLPROPYLOXY)-2,2-DIMETHYLPROPANE, LOT 9250

A 500 ml., three-necked round bottom flask was fitted with a refluxcondenser, a thermocouple, a septum inlet, a magnetic stir bar, and anargon inlet. The flask was charged with3-chloro-2,2-dimethyl-1-propanol, 122.60 grams (1.00 mole, 1.00equivalents), pentane (50 ml.), and 2-methyl-2-butene, 70.66 grams (1.01mole, 1.01 equivalents). This afforded a two phase solution. Thereaction mixture was maintained at 20°-25° C. with a water cooling bath.Boron trifluoride etherate, 13.85 grams (0.098 mole, 0.098 equivalents)was added rapidly via syringe. A mild exotherm, 4°-5° C., ensued, whichsubsided in fifteen minutes. The reaction mixture was stirred at 20°-25°C., and periodically monitored by gas chromatography (GC) for thedisappearance of 3-chloro-2,2-dimethyl-1-propanol. After twenty-fourhours stirring, all the starting material had been consumed, and thereaction mixture was a single phase. The reaction mixture was dilutedwith pentane (50 ml.) and water (100 ml.) and transferred to aseparatory funnel. The aqueous layer was discarded. The organic layerwas washed with saturated sodium bicarbonate solution (2×50 ml.) water(1×50 ml.), and filter-dried over magnesium sulfate. The filtrate wasconcentrated on the rotary evaporator at room temperature to afford aclear, almost colorless liquid, yield=165.90 grams (86.1%).

GC assay=87.7% desired product, 12.3% unknowns. NMR (CDCl₃): 3.45 (s,2H), 3.09 (s, 2H), 1.81-1.20 (m, 2H), 1.09 (s, 6H), 0.95 (s, 6H), and0.84 (t, J=6 Hz, 3H).

5. 1-CHLORO-4-METHOXY-BUTANE, LOT 8663

A one liter, three-necked round bottom flask was equipped with a refluxcondenser, a teflon clad thermocouple, a 225 ml. pressure-equalizingaddition funnel, a large egg-shaped magnetic stir bar, and a gas outletvented to a caustic scrubber. This apparatus was dried in an ovenovernight at 125° C., assembled hot, and allowed to cool to roomtemperature in a stream of argon. The flask was charged with methanol,80.10 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28grams (2.50 moles, 1.00 equivalent). The reaction mixture was cooled to0° C. with a methanol/ice bath, then 356.91 grams (3.00 moles, 1.20equivalents) of thionyl chloride was added dropwise via the additionfunnel. There was an immediate exotherm, and a release of acidic fumes.The temperature was held below 15° C. by adjustment of the feed rate.The total thionyl chloride feed time was two and a third hours. Thecooling bath was removed at the end of the feed. The reaction mixturewas clear and colorless. The reaction mixture was heated to reflux forthree hours, at which time the temperature was 120° C., then thereaction mixture was allowed to cool to room temperature. An aliquot waswithdrawn, diluted with pentane, washed with water and saturated sodiumbicarbonate solution, then analyzed by gas chromatography (30 m.×0.54 mmAT-1 column). Both of the starting materials were still present,tetrahydrofuran (retention time=3.46 minutes), methanol (retentiontime=0.85 minutes), in addition to the desired product (retentiontime=8.68 minutes). The reaction mixture was heated to reflux for anadditional two hours, after which time all gas evolution had ceased. Thereaction mixture was allowed to cool to room temperature, then theorange reaction mixture was transferred to a one liter separatoryfunnel, and diluted with pentane (300 ml.). The organic layer was washedwith water (2×300 ml.), saturated sodium bicarbonate solution (1×300ml.), and finally, water (2×300 ml.). The organic layer was dried(magnesium sulfate), filtered, and purified by distillation through asix inch Vigreux column, at atmospheric pressure. This afforded a clear,colorless oil, yield=187.63 grams (59.8%).

B.P.=140.1°-146.5° C. GC assay=0.28% methanol, 0.17% pentane, 0.64%tetrahydrofuran, 97.68% desired product, and 1.23% unknowns. NMR (D₆Benzene): 3.43-2.89 (m, 4H), 3.12 (s, 3H), and 1.97-1.19 (m, 4H), ppm.

6. 1-CHLORO-3-METHOXY-BUTANE, LOT 8914

A 500 ml., three-necked round bottom flask was equipped with a refluxcondenser, a teflon clad thermocouple, a 125 ml. pressure-equalizingaddition funnel, a large egg-shaped magnetic stir bar, and a gas outletvented to a caustic scrubber. This apparatus was dried in an ovenovernight at 125° C., assembled hot, and allowed to cool to roomtemperature in a stream of argon. The flask was charged with thionylchloride, 124.92 grams (1.05 moles, 1.05 equivalents).3-Methoxy-1-butanol, 104.15 grams (1.00 mole, 1.00 equivalent) was addeddropwise via the addition funnel. There was an immediate exotherm, and arelease of acidic fumes. The total alcohol feed time was thirty-eightminutes. The reaction mixture was dark orange at the end of the feed.The reaction mixture was heated to reflux for four hours, then let coolto room temperature. An aliquot was withdrawn, diluted with pentane,washed with water and saturated sodium bicarbonate solution, thenanalyzed by gas chromatography (30 m.×0.54 mm AT-1 column). All thestarting material had been consumed, with the formation of a slightlyfaster eluting compound (3-methoxy-1-butanol retention time=10.92minutes, product retention time=10.38 minutes). The reaction mixture wastransferred to a one liter separatory funnel, diluted with pentane (300ml.), and the organic layer was washed with water (2×300 ml.), saturatedsodium bicarbonate solution (1×300 ml.), and finally, water (1×300 ml.).The organic layer was dried (magnesium sulfate), filtered, and distilledthrough a twelve inch Vigreux column, at atmospheric pressure. Thisafforded a clear, colorless oil, yield=95.39 grams (77.9%).

B.P.=124.0°-126.6° C. GC assay=1.6% pentane, 94.2% desired product, and4.2% unknowns. NMR (CDCl₃): 3.99-3.43 (m, 3H), 3.35 (s, 3H), 2.13-1.59(m, 2H), and 1.15 (t, J=6 Hz, 3H) ppm.

7. 4-(2-BUTOXY)-1-CHLORO-BUTANE, LOT 8921

A one liter, three-necked round bottom flask was equipped with a refluxcondenser, a teflon clad thermocouple, a 250 ml. pressure-equalizingaddition funnel, a large egg-shaped magnetic stir bar, and a gas outletvented to a caustic scrubber. This apparatus was dried in an ovenovernight at 125° C., assembled hot, and allowed to cool to roomtemperature in a stream of argon. The flask was charged with 2-butanol,185.30 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28grams (2.50 moles, 1.00 equivalent). The reaction mixture was cooled to-15° C., then 356.91 grams (3.00 moles, 1.20 equivalents) of thionylchloride was added dropwise via the addition funnel. There was animmediate exotherm, and a release of acidic fumes. The temperature washeld below 10° C. by adjustment of the feed rate. The total thionylchloride feed time was two and a quarter hours, The cooling bath wasremoved at the end of the feed. The reaction mixture was heated toreflux (95° C.) for six hours, then let cool to room temperature. Analiquot was withdrawn, diluted with pentane, washed with water andsaturated sodium bicarbonate solution, then analyzed by gaschromatography (30 m.×0.54 mm AT-1 column). Both of the startingmaterials were still present, tetrahydrofuran (retention time=6.09minutes), 2-butanol (retention time=6.62 minutes), in addition to thedesired product (retention time=16.78 minutes). The reaction mixture washeated to reflux for an additional four hours, after which time all gasevolution had ceased. The reaction mixture was allowed to cool to roomtemperature, then transferred to a one liter separatory funnel, anddiluted with pentane (300 ml.). The organic layer was washed with water(2×300 ml.), saturated sodium bicarbonate solution (1×300 ml.), andfinally, water (1×300 ml.). The organic layer was dried (magnesiumsulfate), filtered, and purified by distillation from 3.00 grams ofpotassium carbonate through a twelve inch Vigreux column, at atmosphericpressure. This afforded a clear, colorless oil, yield=207.34 grams(50.4%).

B.P.=180.0°-189.6° C. GC assay=96.0% desired product, and 4.0% unknowns.NMR (CDCl₃): 3.72-2.91 (m, 5H), 2.03-1.12 (m, 6H), 0.99 (d, J=6 Hz, 3H),and 0.74 (t, J=6 Hz, 3H) ppm.

8. 1-CHLORO-4-(1-METHYLETHOXY)-BUTANE, LOT 8960

A one liter, three-necked round bottom flask was equipped with a refluxcondenser, a teflon clad thermocouple, a 250 ml. pressure-equalizingaddition funnel, a large egg-shaped magnetic stir bar, and a gas outletvented to a caustic scrubber. This apparatus was dried in an ovenovernight at 125° C., assembled hot, and allowed to cool to roomtemperature in a stream of argon. The flask was charged with 2-propanol,150.25 grams (2.50 moles, 1.00 equivalent) and tetrahydrofuran, 180.28grams (2.50 moles, 1.00 equivalent). The reaction mixture was cooled to0° C., then 356.91 grams (3.00 moles, 1.20 equivalents) of thionylchloride was added dropwise via the addition funnel. There was animmediate exotherm, and a release of acidic fumes. The temperature washeld below 15° C. by adjustment of the feed rate. The total thionylchloride feed time was two and a half hours. The cooling bath wasremoved at the end of the feed. The reaction mixture was heated toreflux (119° C.) for five hours, after which time all gas evolution hadceased, then let cool to room temperature. The orange reaction mixturewas transferred to a one liter separatory funnel, and diluted withpentane (300 ml.). The organic layer was washed with water (2×400 ml.),saturated sodium bicarbonate solution (1×300 ml.), and finally, water(1×300 ml.). The organic layer was dried (magnesium sulfate), filtered,and purified by distillation from 3.00 grams of potassium carbonatethrough a twelve inch Vigreux column, at atmospheric pressure. Thisafforded a clear, colorless oil, yield=234.22 grams (61.8%).

B.P.=160.0°-169.0° C. G.C. assay=88.0% desired products and 12.0%unknowns.

We claim:
 1. A process for the preparation of hydrocarbon solutions ofmonofunctional ether initiators comprising:reacting anomega-protected-1-haloalkyl containing 3 to 35 carbon atoms with aparticulate alkali metal having particle sizes between 10 and 300microns and selected from the group consisting of lithium, sodium andpotassium, at a temperature between 35° and 130° C. in an alkane orcycloalkane solvent containing 5 to 10 carbon atoms to produce acompound of the following structure:

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)                        (II)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium; Z is defined as a branched or straightchain hydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl groups containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkyl amino; R¹, R², and R³ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl groups containing lower alkyl, lower alkoxy, loweralkylthio or lower dialkylamino groups, aryl, and substituted arylgroups containing lower alkyl, lower alkoxy, lower alkylthio or lowerdialkylamino groups.
 2. The process of claim 1 wherein the reactiontemperature is the reflux temperature of the solvent.
 3. The process ofclaim 1 wherein the omega-protected-1-haloalkane is selected from thegroup consisting of 3-(1,1-dimethylethoxy)-1-propylhalide,3-(1,1-dimethylethoxy)-2-methyl-1-propylhalide,3-(1,1-dimethylethoxy)-2,2-dimethyl-1-propylhalide,5-(1,1-dimethylethoxy)-1-pentylhalide,4-(1,1-dimethylethoxy)-1-butylhalide,6-(1,1-dimethylethoxy)-1-hexylhalide,8-(1,1-dimethylethoxy)-1-octylhalide, 4-(ethoxy)-1-butylhalide, 3-3-(dimethylamino)-1-propyloxy!-1-propylhalide, 3-2-(dimethylamino)-1-ethoxy!-1-propylhalide, 3-2-(diethylamino)-1-ethoxy!-1-propylhalide, 3-2-(diisopropyl)amino)-1-ethoxy!-1-propylhalide, 3-2-(1-piperidino)-1-ethoxy!-1-propylhalide, 3-2-(1-pyrrolidino)-1-ethoxy!-1-propylhalide, 4-3-(dimethylamino)-1-propyloxy!-1-butylhalide, 6-2-(1-piperidino)-1-ethoxyl!-1-hexylhalide, 3-2-(methoxy)-1-ethoxy!-1-propylhalide, 3-2-(ethoxy)-1-ethoxy!-1-propylhalide, 4-2-(methoxy)-1-ethoxy!-1-butylhalide, 5-2-(ethoxy)-1-ethoxy!-1-pentylhalide, 3-3-(methylthio)-1-propyloxy!-1-propylhalide, 3-4-(methylthio)-1-butyloxy!-1-propylhalide,3-(methylthiomethoxy)-1-propylhalide, 6-3-(methylthio)-1-propyloxy!-1-hexylhalide, 3-4-(methoxy)-benzyloxy!-1-propylhalide, 3-4-(1,1-dimethylethoxy)-benzyloxy!-1-propylhalide, 3-2,4-(dimethoxy)-benzyloxy!-1-propylhalide, 8-4-(methoxy)-benzyloxy!-1-octylhalide, 4-4-(methylthio)-benzyloxy!-1-butylhalide, 3-4-(dimethylamino)-benzyloxy!-1-propylhalide, 6-4-(dimethylamino)-benzyloxy!-1-hexyihalide,4-(1-propyloxy)-1-butylhalide, 4-(1-methylethoxy)-1-butylhalide,3-(triphenylmethoxy)-2,2-dimethyl-1-propylhalide,4-(triphenylmethoxy)-1-butylhalide, 5-(triphenylmethoxy)-1-pentylhalide,6-(triphenylmethoxy)-1-hexylhalide, 8-(triphenylmethoxy)-1-octylhalide,3-(1,1-dimethylpropyloxy)-1-propylhalide,3-(1,1-dimethylpropyloxy)-2,2-dimethyl-1-propylhalide,4-(1,1-dimethylpropyloxy)-1-butylhalide,6-(1,1-dimethylpropyloxy)-1-hexylhalide, 4-methoxy-1-butylhalide,3-methoxy-1-butylhalide, 3-(triphenylmethoxy)-1-propylhalide, and3-(1,1-dimethylpropyloxy)-2-methyl-1-propylhalide.
 4. The process ofclaim 3 wherein the halide is selected from the group consisting ofbromine and chlorine.
 5. The process of claim 1 wherein the alkali metalis lithium.
 6. Hydrocarbon solutions of monofunctional ether initiatorsof the following structure;

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal; Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl groups containing lower alkyl, loweralkoxy, lower alkylthio, or dialkylamino, and R¹, R² and R³ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl groups containing lower alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino groups, aryl, and substituted arylgroups containing lower alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino groups.
 7. The monofunctional ether initiators of claim 6wherein M is lithium, Z is a straight chain hydrocarbon group containing3 carbon atoms, and R¹, R² and R³ are methyl groups.
 8. Themonofunctional ether initiators of claim 6 wherein M is lithium, Z is astraight chain hydrocarbon group containing 4 carbon atoms, and R¹, R²,and R³ are methyl groups.
 9. The monofunctioal ether initiators of claim6 wherein M is lithium, Z is a straight chain hydrocarbon groupcontaining 6 carbon atoms, and R¹, R², and R³ are methyl groups.
 10. Themonofunctional ether initiators of claim 6 wherein M is lithium, Z is astraight chain hydrocarbon group containing 8 carbon atoms, and R¹, R²and R³ are methyl groups.
 11. The monofunctional ether initiators ofclaim 6 wherein M is lithium, Z is a straight chain hydrocarbon groupcontaining 3 carbons, and R¹ and R² are methyl groups and R³ is an ethylgroup.
 12. A functionalized polymer produced by a process comprising thesteps of:a) initiating polymerization of a conjugated polyenehydrocarbon or an alkenyl substituted aryl hydrocarbon having 4 to 30carbon atoms in a hydrocarbon or mixed hydrocarbon-polar solvent mediaat a temperature of 10°-70° C. with an initiator having the formula

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium, Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkylamino, and R¹, R² and R³ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl containing lower alkyl, lower alkoxy, lower alkylthioor lower dialkylamino, aryl, and substituted aryl containing loweralkyl, lower alkoxy, lower alkylthio or lower dialkylamino, to producean intermediate polymer, b) reacting the intermediate polymer with afunctionalizing compound, and c) optionally hydrogenating the polymer.13. A process for the anionic polymerization of an anionicallypolymerizable monomer comprising the steps of:a) initiatingpolymerization of a conjugated polyene hydrocarbon having 4 to 30 carbonatoms or a vinylsubstituted aromatic hydrocarbon in a hydrocarbon ormixed hydrocarbon-polar solvent media at a temperature of 10°-70° C.with an initiator having the formula

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium; Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkylamino; and R¹, R² and R³ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl groups containing lower alkyl, lower alkoxy, loweralkylthio, or lower dialkylamino groups, aryl, and substituted arylgroups containing lower alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino groups to produce an intermediate polymer and b) reactingthe intermediate polymer with a functionalizing compound to produce afunctionalized polymer c) optionally hydrogenating the functionalizedpolymer d) further reacting the functionalized polymer with one or morecomonomers in the presence of a strong acid catalyst to simultaneouslydeprotect the polymer and polymerize the comonomers at both functionalsites or e) further reacting the functionalized polymer with othercomonomers in the absence of strong acid catalysts, then deprotectingthe resultant copolymer and f) further reacting the resultant copolymerwith the same or other comonomers.
 14. The process of claim 13 whereinsaid functionalizing compound is selected from the group consisting ofethylene oxide, carbon dioxide, 1,5-diazabicyclo (3.1.0) hexane,N-benzylidene trimethylsilylamide, sulfur, omega-alkenylarylhalosilanes,isomeric divinylbenzenes, chlorosilanes, and chlorostannanes and whereinthe process further comprises recovering a functionalized linear orbranched polymer having one or more terminal functional groups.
 15. Theprocess of claim 14, further comprising hydrogenating the recoveredpolymer of claim 14 to produce hydrogenated polymer.
 16. The process ofclaim 13 wherein the conjugated polyene hydrocarbon is a conjugateddiene hydrocarbon selected from the group consisting of 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene (piperylene),2-methyl-3-ethyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 1,3hexadiene,2,5-dimethyl-2,4-hexadiene and 1,3-octadiene.
 17. The process of claim13 wherein the polar solvent is selected from the group consisting ofdiethyl ether, triethylamine, methyl tert-butyl ether, dibutyl ethersand tributylamine.
 18. The process of claim 14 further comprisingreacting the polymers of claim 14 produced from isomeric divinylbenzenes and deprotecting the resulting polymer to yield star-branchedpolymers with hydroxy-terminated branches.
 19. The process of claim 18wherein the star-branched polymers are hydrogenated.
 20. The process ofclaim 19 further comprising reacting the hydrogenated deprotectedpolymers of claim 19 with ethylene oxide and potassium alkoxides toproduce hydrogels.
 21. The process of claim 20 further comprisingreacting the hydrogenated and deprotected polymers of claim 20 withacryloyl chloride and methacryloyl chloride.
 22. The process of claim 21further comprising reacting the polymers of claim 21 with alkylacrylates, alkyl methacrylates or dialkylacrylamides to producehydrogels.
 23. The process of claim 14 wherein the functionalizingcompound is ethylene oxide, the functionalized polymer is hydrogenated,and the comonomers are selected from the group consisting ofepichlorohydrin and diisocyanates to produce epoxide andisocyanate-terminated polymers.
 24. The process of claim 23 furthercomprising simultaneous deprotecting and polymerizing the isocyanate andepoxy-terminated polymers.
 25. The process of claim 14 wherein saidfunctionalizing compound is ethylene oxide and wherein said processfurther comprises hydrogenating said polymer and reacting saidhydrogenated polymer with comonomers selected from the group consistingof dialkylterephthalates, alpha-omega alkane diols, diisocyanates,caprolactam and adipic acid, wherein the polymerization is carried outsimultaneously with deprotection.
 26. The process of claim 14 whereinthe functionalizing compound is ethylene oxide, the comonomer isethylene oxide, the polymerization is carried out in the presence ofpotassium tert-butoxide, the resulting copolymer is deprotected andreaction with comonomer continued.
 27. The process of claim 14 whereinsaid functionalizing compound is ethylene oxide, the functionalizedpolymer is hydrogenated and reacted with a diisocyanate in a 2:1 ratio,further reacted with hydroxyethylacrylate in the presence of a basiccatalyst, and deprotected to yield a macromonomer.
 28. The process ofclaim 14 wherein the functionalizing compound isstyrenyldimethylchlorosilane.
 29. A functionalized polymer produced by aprocess comprising the steps of:a) initiating polymerization of aconjugated polyene hydrocarbon or an alkenyl substituted arylhydrocarbon having 4-30 carbon atoms in a hydrocarbon or mixedhydrocarbon-polar solvent media at a temperature of 10°-70° C. with aninitiator having the formula

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium, Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms optionally containingaryl or substituted aryl containing lower alkyl, lower alkoxy, loweralkylthio or lower dialkylamino, and R¹, R² and R³ are independentlyselected from the group consisting of hydrogen, alkyl, substituted alkylcontaining lower alkyl, lower alkoxy, lower alkylthio or lowerdialkylamino, aryl, and substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkylamino to produce an intermediatepolymer, b) reacting the intermediate polymer with a functionalizingcompound to form a star-branched polymer, c) hydrogenating thestar-branched polymer, d) further reacting the star-branched polymerwith ethylene oxide or a potassium alkoxide in the presence of a strongacid to simultaneously deprotect and polymerize the functionalizedpolymer or e) further reacting the star-branched polymer with ethyleneoxide or a potassium alkoxide in the absence of a strong acid catalyst,followed by deprotection and further reaction with said ethylene oxideor potassium alkoxide, and f) further reacting the hydrogenated anddeprotected polymers with acryloyl chloride or methacryloyl chloride.30. A functionalized polymer produced by a process comprising the stepsof:a) initiating polymerization of a conjugated polyene hydrocarbon oran alkenyl substituted aryl hydrocarbon having 4-30 carbon atoms in ahydrocarbon or mixed hydrocarbon-polar solvent media at a temperature of10°-70° C. with an initiator having the formula

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium, Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkylamino, and R¹, R² and R³ areindependently selected from hydrogen, alkyl, substituted alkylcontaining lower alkyl, lower alkoxy, lower alkylthio, or lowerdialkylamino, aryl, or substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio, or lower dialkylamino to produce anintermediate polymer, b) reacting the intermediate polymer with afunctionalizing compound to form a star-branched polymer, c)hydrogenating the star-branched polymer, d) further reacting thestar-branched polymer with ethylene oxide or a potassium alkoxide in thepresence of a strong acid to simultaneously deprotect and polymerize thefunctionalized polymer or e) further reacting the star-branched polymerwith ethylene oxide or a potassium alkoxide in the absence of a strongacid catalyst, followed by deprotection and further reaction with saidethylene oxide or potassium alkoxide, and f) further reacting thehydrogenated and deprotected polymer with an alkyl acrylate, alkylmethacrylate or dialkylacrylamides.
 31. A functionalized polymerproduced by a process comprising the steps of:a) initiatingpolymerization of a conjugated polyene hydrocarbon or an alkenylsubstituted aryl hydrocarbon having 4-30 carbon atoms in a hydrocarbonor mixed hydrocarbon-polar solvent media at a temperature of 10°-70° C.with an initiator having the formula

    M--Z--O--C(R.sup.1 R.sup.2 R.sup.3)

wherein M is an alkali metal selected from the group consisting oflithium, sodium and potassium, Z is a branched or straight chainhydrocarbon group which contains 3-25 carbon atoms, optionallycontaining aryl or substituted aryl containing lower alkyl, loweralkoxy, lower alkylthio or lower dialkylamino, and R¹, R² and R³ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl containing lower alkyl, lower alkoxy, lower alkylthio,or lower dialkylamino, aryl, or substituted aryl containing lower alkyl,lower alkoxy, lower alkylthio, or lower dialkylamino to produce anintermediate polymer, b) reacting the intermediate polymer with ethyleneoxide, c) hydrogenating the polymer, d) reacting the hydrogenatedfunctionalized polymer with diisocyanate in a 2:1 ratio diisocyanate tohydrogenated functionalized polymer, e) further reacting the polymerwith hydroxyethylacrylate in the presence of a basic catalyst, and f)deprotecting the polymer.